Process for breaking petroleum emulsions



UNITED STATES PATENT OFFICE- PROCESS FOR BREAKING PETROLEUM EMULSIONS' I Melvin De Groote, University City, and Bernhard Keiser, Webster Groves, Mo., assignors to Petrolite Corporation, Ltd., Wilmington, Del., a corporation of Delaware No Drawing. Application October 20, 1941, Serial No. 415,764

6 Claims. (Cl. 252-344) This invention relates primarily to the resO- atom; RCO denotes an acyl radicalderi'ved from lution of petroleum emulsions. l a detergent-forming monocarboxy acid, with a One obJect of our invention is to provide a heterocyclic compound of the pyridine, quinoline, novel process for resolving petroleum emulsions isoquinoline series, and C-methyl homologs of the water-in-oil yp that are mmonly rethereof, in the presence of substantially one mole ferred to as cut oil, roily o-il, "emulsified of halogen'hydride at an elevated temperature,

and wh ch O D fi p s of the hetero'cyclic compound being applied in an P Y- H Waters 01 br e-S d per amount substantially equivalent to the halogen In a more or less permanent state throughout hydride, and usually in excess thereof, i. e., the the 011 which constltutes the continuous phase 10 t n being ndu ted in the presence of the 0f the emulsion. free base Another object Of our inven to Provide It is well known that certain monocarbox'y an economical and rapld D O SS for Separating organic acids containing eight carbon atoms or 9111111810115 have been p pa ed de 6011- more, and not more than 32 carbon atoms, are oued condltlons fTOIII mineral such as ude 15 characterized by the fact that they combine with petroleum and relatively soft waters or weak lkalis to produce soap or soap-like materials. brmes. Controlled emulslficatlon and SubSe- These detergent-forming acids include fatty (men? demu 1S1ficat1 n finder the conditions just acids, resin acids, petroleum acids, etc. For the f q l d 15 mfican V ue i removing sake of convenience, these acids will be indicated nnpurlties, particularly inorganic salts, from by the formula R.COOH. Certain derivatives of pipehne 011. detergent-forming acids react with alkali to pro- The fiemulslfiel' dem1 11s1fy1ng agent duce soap or soap-like materials, and are the ob- Ployed m 0111' P P a quaternary vious equivalent of the unchanged orunmodified p n f th p r me serles 0f h kind detergent-forming acids; for instance, instead hereinafter descnbed in detail. Members of the of fatty acids, n might employ the chlorinat pynd ne series smta l as r a an s in ude fatty acids. Instead of the resin acids, one might pyridine, alkylated derivatives of pyridine, paremploy th hydrogenated resin acids. Instead ticularly alkylated derivatives in which the alkyl of naphthenic acids, one might employ bromiradical contains three carbon atoms or less, and nated naphthenic acids, tc,

especially methylated pyridines, i. e., pyridines The fatty acids are of the type commonly re-' in which one, two, or three methyl groups have ferred.to higher fatty acids; and of course,

been substituted in the nucleus, such as picolines; this is also t i regard to derivatives of t lutldmes and A150 Suitable as reactkind indicated, insofar that such derivatives are ants are the comparable quinolines and isoquin obtained from higher fatty acids. The petroleum lines, along with C-methyl l omologues thereof. acids d d not only naturally-occurring naph- Coal bases represent mlxtures of Suitable thenic acids, but also acids obtained by the ox,- heterocyclic materials which may be used as idation of gwin, etc, such acids may such, or after suitable purification, without sepahave as many as 32 carbon atoms, for instance, ration into the individual components. see U s t t No. 2 242 37 t d M 20 Specifically, then, compounds herein contem- 40 1941, to Shie1ds o plated as demulsifiers, consist of the quaternary As to a description of e hat analogous nitrogen products obtained by reacting one mole type f compound, See s Patent No. 2,242,211, of hydroxy compounds of the fm'mma: dated May 20, 1941, to 'Haack. See also our co- T H pending application for Patent Serial .No. 401,375, R'Co filed July '7, 1941, which subsequently matured as U. S. Patent No; 2,273,181, dated February H 17, 1942, to" De Groote and Keiser.

in which T is a member of the class consisting of Certain amines 6 available raw materials' hydrogen atoms and hydroxyethyl radicals, and 5 for the manufacture of amides employed as T is a member of the class consisting of hydroactants in the manufacture of the demulsifiers gen atoms, methyl radicals, ethyl radicals, and 01 new c mpounds he e contemplated- It is hydroxymethyl radicals, with the proviso that at well known that parafiins can be treated with least one occurrence of 'I" is a radical of the kind nitric acid, so as to produce nitroparaifins or designated, as difierentiated from a hydrogen nitrites. Such nitroparafiins can be treated with scribed are:

2-amino-1-butanol NH: CHgCHaJIHCHaOH Z-amino-Z-methyl-l-propanol CH: CHsOH 2-amino-2-methyl- 1,3-propanedio1 2-amino-2-ethy1-1,3-propanediol NH: no-cm--cmon Tris (hydroxymethyl) aminomethane NH2C(CH20H):

Rearranging such formulas, in an unconventional form designed to show that in each case a single carbon atom separates the amino nitrogen atom from a hydroxymethyl radical, one obtains the following formulas:

Is such amines are treated with ethylene oxide, so as to convert such primary amines into secondary amines, one obtains compounds of the following type:

H 511 onclm Hon N-- c-on H/ H NC-OH n a H H on 011cm. Hen

\N -c-on H/ 23H:

on OHCSHI Hon N-cc-on H/ as.

on once! mlsn Such primary or secondary amines can readily be converted into the corresponding amide by reaction with a selected monocarboxy detergent-forming acid or the functional equivalent of the acid, such as anhydride, acyl chloride, amide or ester. The procedure employed for the manufacture of such amides is well known. Briefly stated, the reactants are heated at a temperature to permit evolution of water, ammonia, hydrochloric acid, etc., and such reactions are obviously conducted at a point below the decomposition temperature. Employing such procedure, one can readily obtain amides, or better still, substituted amides of the following types:

T..CO non H )riz-g-on 11 lion 2 as q H I aco Hon H HCH RCO HH OHCZHA/ It may be well to point out that where an amide is derived from a primary-amine, such amide. may be treated under proper conditions with ethylene oxide to yield hydroxyethyl derivatives. Such compounds so obtained are identical with the amides derived by reaction between the from petroleum acids, rosin acids, and the like. I

We have found that by far the most effective demulsifying agents are obtained from unsatu-. rated fatty acids having 18 carbon atoms. Such unsaturated fatty acids include the fatty acids, such as oleic acid, ricinoleic acid, linoleic acid, linolenic acid, etc. One may employ mixed fatty acids, as, for example, the fatty acids obtained from hydrolysis of cottonseed oil, soyabean oil. corn oil, etc. Our preferred demulsifier is obtained from unsaturated fatty acids, and more especially, unsaturated fatty acids containing a hydroxyl radical, .or unsaturated fatty acids which have been subjected to an oxidation or oxyalkylation step, such as oxyethylation.

In view of what has been said, and particularly by reference to the aforementioned Haack patent, it will be noted that compounds'of the type herein contemplated as demulsifiers, may be indicated by the following formula:

Halogen DEN in which Tis a member of the class consisting of hydrogen atoms and hydroxyethyl radicals, and T is a member of the class consisting of hydrogen atoms, methyl radicals, ethyl radicals, and hydroxymethyl radicals, with the proviso that at least one occurrence of T' is a radical of the kind designated as differentiated from a hydrogen atom; RC0 is an acyl radical derived from a monocarboxy detergent-forming acid, having at least 8 and not more than 32 carbon atoms;

and DEN represents a heterocyclic compound of the pyridine series consisting of pyridine, quinoline, isoquinoline, thereof. The halogen, of course, is most suitably chlorine or bromine; but iodine may be employed except for its excessive cost. More correctly, DEN is contemplated as a radical, rather than a compound.

Compositions of the kind intended to be used as the demulsifying agent in our'process, may be exemplified by the following examples.

Example 1 560 g. of a fatty acid amide, obtained by reaction' of split cocoanut oil (containing all the natural acids, beginning with the capric up to the stearic acid, and some oleic acid) with tris(hydroxymethyl)aminomethane, 330 g. hydrochloride of a fraction of pyridine bases (50% distilling up to 140 C. distilling up to 160 completely soluble in water) and g. of the mixture of the free pyridine bases, are heated at 100 C. until the product is, for the most part,

soluble in water and stable towards diluted sodium carbonate solution. After being yseparated from the primary compounds not reacted upon,

the mixture of pyriminium-, picoliniumand other homologous pyridinium compounds obtained, may be further worked up to form a 10% watery solution.

When working at 150460", the reaction is more rapid.

Furthermore, pure pyridine may be used instead of a mixture of pyridine bases.

(Compare with Example'2 of the aforementioned Haack Patent No. 2,242,211).

Example 2 I The substituted ricinoleoamide derived by reaction between -ricinoleic acid and tris(hydroxymethyhaminomethane is substituted for the amide employed in Example 1, preceding.

Example 3 A drastically oxidized castor' oil having approximately the following characteristics:

is converted into the' substituted amide by reaction with tris(hydroxymethyl) aminomethane. Such amide is substituted for the amide employed in Example 1, preceding.

Example 4 One pound mole of castor oil is treated with three pound moles of ethylene oxides in the presence of one-half of 1% of sodium rlcinoleate as a catalyst at a temperature of 100-200 C. at a gauge pressure of 100 pounds and less than 300 pounds, soas to produce an oxyethylated triricinolein. An amide derived from such materialby reaction with tris(hydroxymethyl)- aminomethane is employed instead of the amide described in Example 1, preceding.

Example 5 Phenylstearic acid is prepared in any suitable manner, as, for example, in the manner and C-methyl homologs' diluents.

described in U. S. Patent No. 2,081,075, dated May 18, 1937, to Vobach. This is converted into an amide by reaction with tris(hydroxymethyl) aminomethane, and such amide employed in the manner described in Example 1, preceding.

Example 6 In Examples 1 to 5, preceding, the amide derived from 2-amino-2-methyl-l-propanol is used instead of the amide derived from tris(hydroxymethyl) aminomethane.

Example 8 In Examples 1 to 5, preceding, the amide derived from Z-amino-Z-methyl-1,3-propanediol is used instead of the amide derived from tris- (hydroxymethyl) aminomethane.

Example 9 In Examples 1 to 5, preceding, the amide derived from 2-amino-ethyl-1,3-propanediol is used instead of the amide derived fmm tris- (hydroxymethyl) aminomethane.

The manufacture of the above compounds is usually conducted with an excess of the pyridinium base halide, such as the hydrochloride, or hydrobromide, and usually in the presence of a significant amount of the free pyridim'um base itself. In many instances, however, there is no need to use an excess of the pyridinium base halide, and, in fact, no need to have present any of the free pyridinium base itself, or, at the most, only a trace of the free base.

Sometimes the reaction with the pyridinium compound can be catalyzed by the presence of small amounts of soaps or alkalis. As is obvious, other monovalent anions may replace the halogen and serve as a functional equivalent.

Conventional demulsifying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such as water; petroieum hydrocarbons, such as gasoline, kerosene, stove oil; a coal tar product, such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oils, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents, such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc., may be employed as- Similarly, the material or materials employed as the demulsifying agent of our process may be admixed with one'or more of the solvents customarily used in connection with conventional demulsifying agents. Moreover, said material or materials may be used alone, or in admixture with other suitable well known cl ssne of demulsifying agents.

It is well known that conventional demulsifying agents may be used in a water-soluble form, or in an oil-soluble form, or in a form exhibiting both oil and water solubility. Sometimes they may be used in a form which exhibits relatively limited oil solubility. However, since such reagents are sometimes used in a ratio of 1 to 10,000, or 1 to 20,000, or even 1 to 30,000, such an apparent insolubility in oil and water is not significant, because said reagents undoubtedly have solubility within the concentration employed. This same fact is true in regard to the material or materials employed as the demulsifying agent of our process.

We desire to point out that the superiority of the reagent or demulsifying agent contemplated in our proces is based upon its ability to treat certain emulsions more advantageously and at a somewhat lower cost than is possible with other available demulsifiers, or conventional mixtures thereof. It is believed that the particular demulsiiying agent or treating agent herein described will find comparativay limited application, so far as the majority of oil field emulsions are concerned; but wehave found that such a demulsifying agent has commercial value, as it will economically break or resolve" oil field emulsions-in a number of cases which cannot be treated as easily or at so low a cost with the demulsifying agents heretofore available.

In practising our process, a treating agent or demulsifying agent of the kind above described is brought into contact with or causedto act upon the emulsion to be treated, in any of the various ways, or by any of the various apparatus now generally used to resolve or break petroleum emulsions with a chemical reagent, the above procedure being used either alone, or in combination with other demulsifying procedure, such as the electrical dehydration process.

The demulsifier herein contemp e y be employed in connection with what is commonly known as down-the-hole procedure, i. e., bringin the demulsifier in contact with the fluid of the well at the bottom of the well or at some point prior to the emergence of said well fluids. This particular type of application is decidedly feasible when the demulsifier is used in connection with acidification of calcareous oil-bearing strata, especially if suspended in or dissolved in the acid employed for acidification.

Attention is directed to our co-pending application for patent, Serial No. 401,375, filed July 7, 1941, which subsequently matured as U. S. Patent No. 2,273,181, dated February 17, 1942, to De Groote and Keiser. Said co-pending application contemplates resolution of petroleum emulsions of the water-in-oil type by means of demulsifiers of the following formula type:

Halogen CHi-CHr-NILO 0.12.

in which the acyl radical RC0 is derived from a. monocarboxy detergent-brazing acid having at least 8 carbon atoms and not more than 32 carbon -atoms; and DEN represents a heterocyclic.

compound of the pyridine series consisting of pyridine, quinoline, isoquinoline. and C-methyl homologs thereof. The halogen, of course, is most suitably chlorine or bromine; but iodine may be employed except for its excessive cost. More correctly, DEN is contemplated as a radical, rather than a compound. Attention is also directed to our co-pending applications, filed the same date as the instant application, and bearing the following serial numbers: 415,763, 415,765 and 415,766.

Having thus described our invention, what w claim as new and desire to secure by LettersPatcut is:

1. A process for breaking petroleum emulsions of the water-in-oil type, which consists in subjecting the emulsion to the action of a demulsifier comprising a chemical compound of the following formula:

Halogen CH:C-NT.0C.R

in which T is amember of the class consisting of hydrogen atoms and hydroxyethyl radicals, and T is a member of the class consisting of methyl radicals, ethyl radicals, and hydroxymethyl radicals, with the proviso that at least one occurrence of T is a radical of the kind designated, and differentiated from a hydrogen atom; RC is an acyl radical derived from a monocarboxy detergent-forming acid having at least 8 and not more than 32 carbon atoms; and DEN represents a radical of a heterocyclic compound of the pyridine series consisting of pyridine, quinoline, isoquinoline, and C-linked methyl homologues thereof.

2. A process for breaking petroleum emulsions of the water-in-oil type, which consists in sub- .iecting the emulsion to the action of a demulsifier comprising a chemical compound of the following formula:

Halogen cyclic compound of the pyridine series consisting of pyridine, quinoline, isoquinoline, and C-linked methyl homologues thereof.

4. A process for breaking petroleum emulsions of the water-in-oil type; which consists insub-- jecting the emulsion to the action of a demulsifler comprising a chemical compound of the following formula:

Halogen D E I CHz-%NT.O 0.12

in which T is a member of the class consisting of hydrogen atoms and hydroxyethyl radicals, and 'I" is a member of the class consisting of methyl radicals, ethyl radicals, and hydroxymethyl radicals, with the proviso that at least one occurrence of T is a radical of the kind designated, and difierentiated from a hydrogen atom; RC0 is a ricinoleyl radical; and DEN represents a radical of a heterocyclic compound of the pyridine series consisting of pyridine, quinoline, isoquinoline, and C-linked methyl homologues thereof.

5. A process for breaking petroleum emulsions of the water-in-oil type, which consists in subjecting the emulsion to the action of a demulsifier comprising a chemical compound of the following formula:

in which T is a member of the class consisting of hydrogen atoms and hydroxyethyl radicals, and I" is a member of the class consisting of methyl radicals, ethy1 radicals, and hydroxymethyl radi-' cals, with the proviso that at least one occurrence of 'I" is a radical of the kind designated, and

differentiated from a hydrogen atom; RC0 is an .oleyl radical; and DEN represents a radical of a heterocy'clic compound of the pyridine series consisting of pyridine, quinoline, isoquinoline, and

. C-linked methyl homologues thereof.-

3. A process for breaking petroleum'emulsions of the water-in-oil type. which consists in subjecting the emulsion to the action of a demulsifler comprising a chemical compound of the following formula:

Halogen.

cm-c-muocn in which T'is a mmber of the class consisting of hydrogen atoms and hydroxyethyl radicals, and T is a member of the class consisting of methyl radicals, ethy1 radicals, and hydroxymethyl radicals, with the proviso that at least one occurrence of T is a radical of the kind designated, and differentiated from a hydrogen atom; RC0 is an acyl radical derived from unsaturated higher fatty acid having at least 8 and not more than 32 carbon atoms; and DEN represents a radical of a heterocyclic compound of the pyridine series consisting of pyridine. quinoline. isoquinoline. and (l-linked methyl homologues thereof.

6. A process for breaking petroleum emulsions otthe water-in-oil type, which consists in subjecting the emulsion to the action of a demulsifler comprising a chemical compound of the following formula:

Halogen FT, o I in which T is a member of the class consisting of hydrogen atoms and hydroxyethyl radicals, and

T' is a member of the class consisting of methyl radicals, ethyl radicals, and hydroxymethyl radicals, with the proviso that at least one occurrence of '1" is a radical of the kind designated. and diflerentiatedfrom. a hydrogen atom; RC0 is a linoleyl radical; and DEN represents a radical of a-heterocyclic compound ofthe pyridine series consisting of pyridine, quinoline, isoquinoline, and C-linked methyl homologues thereof.

DE oRoo'rE. BERNHARD nmsna, 

